AB Stacking Boundaries in Bilayer Graphene - Nano Letters (ACS

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AC/AB Stacking Boundaries in Bilayer Graphene Junhao Lin, Wenjing Fang, Wu Zhou, Andrew R Lupini, Juan Carlos Idrobo, Jing Kong, Stephen J. Pennycook, and Sokrates T. Pantelides Nano Lett., Just Accepted Manuscript • DOI: 10.1021/nl4013979 • Publication Date (Web): 17 Jun 2013 Downloaded from http://pubs.acs.org on June 18, 2013

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AC/AB Stacking Boundaries in Bilayer Graphene Junhao Lin†,‡, Wenjing Fang , Wu Zhou‡,*, Andrew R. Lupini‡, Juan Carlos Idrobo‡, ║

Jing Kong , Stephen J. Pennycook‡, Sokrates T. Pantelides†,‡ ║

†Department of Physics and Astronomy, Vanderbilt University, Nashville, TN 37235, USA ‡Materials Science & Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA ║Department of Electrical Engineering and Computer Science, Massachusetts Institute of Technology, Cambridge, MA 02139, USA * Email: [email protected]

ABSTRACT: Boundaries, including phase boundaries, grain boundaries, and domain boundaries, are known to have an important influence on material properties. Here, dark-field (DF) transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM) imaging are combined to provide a full view of boundaries between AB and AC stacking domains in bilayer graphene across length scales from discrete atoms to the macroscopic continuum. Combining the images with results obtained by density functional theory (DFT) and classical molecular dynamics calculations, we demonstrate that the AB/AC stacking boundaries in bilayer graphene are nanometer-wide strained channels, mostly in the form of ripples, producing smooth lowenergy transitions between the two different stackings. Our results provide a new understanding of the novel stacking boundaries in bilayer graphene, which may be applied to other layered twodimensional materials as well.

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Bilayer graphene, stacking boundary, dark-field TEM, STEM imaging, density

functional theory, classical molecular dynamics

Bernal stacked bilayer graphene (BLG) has been the subject of extensive research because of its tunable bandgap and promising application in optoelectronics and nanoelectronics

1, 2

. Besides

the well-studied grain boundaries in each graphene layer, which have been shown to affect the mechanical properties and transport performance of monolayer graphene

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, unique stacking

boundaries can be present in Bernal stacked BLG at the interfaces of domains with the same crystal orientation but different stacking, i.e. AB and AC stacking. Here, the terms AB and AC stacking refer to shifting one of the graphene layers in opposite directions along 1/3 of the [1, 1] crystallographic vector, respectively, as schematically shown in Figure 1.

Evidence for the co-existence of domains with mirrored AB and AC stackings was reported recently in BLG synthesized via silicon carbide (SiC) thermal decomposition and chemical vapor deposition (CVD) growth

7, 8

. However, unlike grain boundaries, the presence of stacking

boundaries in BLG does not seem to cause severe degradation of the transport performance of BLG-based devices

2, 9, 10

. Moreover, the detailed structure of such stacking boundaries has not

been investigated. In particular, it is not known if the stacking boundaries are atomically sharp like grain boundaries. As an important step to reveal the contribution of the stacking boundaries to the properties of BLG, visualizing the morphology and identifying the atomic structure of these unique boundaries is necessary.


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In this Letter, we combine dark field (DF) imaging on TEM and STEM, bridging scales from several microns down to the atomic level, to systematically analyze the morphology of stacking boundaries in Bernal stacked BLG. Complemented by density functional theory (DFT) calculations and classical-potential molecular dynamic modeling, we demonstrate that the stacking boundaries are not atomically sharp but, instead, are nanometer-wide strained channels appearing mostly in the form of ripples, which result in smooth transitions between the mirrored AB and AC stackings. Our results provide a full view of these coherent stacking boundaries in layered two-dimensional materials.

In order to identify the AB/AC stacking boundaries, we performed tilted DF-TEM experiments 11 on high quality BLG grown on Cu foil via an optimized CVD method

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. A large flake of

oriented bilayer graphene (oBLG) with a size over 10 µm is shown in Figure 2a. The relative AB and AC stacking domains in this region are revealed by tilted DF-TEM images acquired using the first-order diffraction spot (0, 1), based on their mirror-symmetrical intensity variations during tilting

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(details in Figure S1). For better visibility, the AB and AC stacking domains

were false-colored and reconstructed into a single image (Figure 2b). Noticeably, areas with densely packed AB and AC stacking domains can often be observed, as highlighted by the red rectangles.

Magnified views of a selected oBLG region of Figure 2b (black square) are shown in Figures 2c2e, where the relative AB and AC stacking domains obtained via tilted DF-TEM imaging are shown in Figure 2c and 2d. These ordered stacking domains are typically micrometer-long strips with widths of a few tens to a few hundred nanometers. Using the second order diffraction spot


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(-1,1), the boundaries between domains appear as dark lines in the DF-TEM image acquired at zero tilt (Figure 2e), while the AB and AC stacking regions are bright and indistinguishable under this imaging condition. The contrast difference indicates a decrease of the (-1, 1) diffraction intensity at the boundary regions as compared to ordered AB/AC stacking regions. The widths of the stacking boundaries are estimated to be ~10 nm from the DF-TEM images (Figure S2), suggesting the possible presence of nm-wide transition regions between the two stacking domains. Further, we notice that the stacking boundaries have overall random orientations and display a wide range of image contrast with some being darker than others, indicating that the stacking boundaries may have diverse morphologies depending on their precise formation conditions. These dark lines are absent in monolayer regions (as shown in Figure S3).

The structure-induced intensity decrease at stacking boundaries in DF-TEM images can be explained through the interference of the diffracted electron beam when transmitting through the BLG. DF-TEM images are formed by specific scattered electrons; therefore, the behavior of the image intensity mainly depends on the diffraction peak being used, corresponding to a specific lattice periodicity. The first- and second-order diffraction peaks for monolayer graphene (Figure S1c) correspond to lattice periodicities of 2.13 Å and 1.23 Å, respectively, as schematically shown in Figure 1a. For oBLG where the two layers adopt the same crystal orientation, the diffraction from each layer interferes with each other. Therefore, the DF-TEM image intensity is controlled by the phase difference between the electron waves scattered by the two layers (or in other words, the relative shift of the lattice periodicity between the two layers) 11. For example, the mirrored intensity variation of AB and AC stacking (Figure 2c & 2d) is due to the anti-


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symmetrical phase factor generated by the opposite relative shift of the 2.13 Å lattice periodicity during tilting (See Figure S1e & S1f for details).

For perfect AB and AC stackings, the interference of electrons scattered by the 1.23 Å lattice periodicities from both layers is fully constructive (∆x1=0, see Figure 1b), making them indistinguishable in the DF-TEM image shown in Figure 2e. The reduced image contrast at the stacking boundaries (dark lines in Figure 2e), thus, indicates a phase difference (i.e. a non-zero ∆x1) at these transition regions. This phase shift could in principle be induced by: i) reconstruction along the AB and AC stacking domains due to the presence of sharp stacking boundaries; or ii) a continuous relative shift between the two layers by straining one of the two layers, as will be discussed. Furthermore, the variation in image contrast (Figure 2e) for the stacking boundaries suggests that different amount of shifts in lattice periodicity (∆x1) can be present between the two layers at the transition regions, leading to different morphologies.

In order to resolve which of these two different classes of boundary accounts for the DF-TEM contrast, the atomic structure of stacking boundaries is further investigated using annular darkfield (ADF) imaging on an aberration-corrected Nion UltraSTEM-100 operated at 60 kV 13. The ADF images can be approximately interpreted as the convolution of the projected atomic positions in both graphene layers and the small electron probe. For better visibility, all ADF images shown in the main text have been Fourier filtered using a hexagonal mask in the FFT pattern (see details in Figure S4 and the as-acquired images are provided in Figure S5). Figure 3b shows a filtered ADF image for a perfect AB stacking domain, with half of the carbon atoms overlapped. The brighter spots are the overlapping sites of two carbon atoms, illustrated by the


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atomic model shown in the upper inset. The lower inset of Figure 3b shows a simulated ADFSTEM image for perfect AB stacking which reproduces the regular pattern observed experimentally.

Besides the regular hexagonal AB (or AC) stacking pattern, irregular Moiré patterns are always observed at the transition regions of the stacking boundary. Figure 3a shows a Fourier filtered ADF image of a stacking boundary (See Figure S6 for a lager field of view of the stacking boundary without filtering). AB and AC stacking domains can be seen on both ends, while the transition region displays continuously varying dot-like Moiré pattern in the middle (red rectangle). Only one set of diffraction spots can be obtained from the Fourier transform of the whole image (inset in Figure 3a), suggesting that these irregular Moiré patterns are generated via a gradual shift between the two layers without a mis-orientation angle. Importantly, the irregular Moiré patterns continue over a width of several nanometers, which is consistent with the nanometer-wide dark lines (stacking boundaries) observed in DF-TEM images. Moreover, different types of irregular Moiré patterns can be found in the stacking boundary regions. For instance, Figure 3c & 3d show wiggle-like and square-like Moiré patterns with a gradual transition to regular AB/AC stacking regions. The observed irregular Moiré patterns can have a variety of different orientations with respect to the graphene lattice, as illustrated by the red hexagons in each figure.

The observation of gradually changing Moiré patterns over transition regions of a few nanometers demonstrates that the stacking boundaries are not atomically sharp, as further confirmed by DFT calculations detailed in Figure S7, but are indeed continuous transitions from


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AB to AC stacking with gradual lattice deformation. The multitudinous irregular Moiré patterns can also be associated with the wide range of DF-TEM image contrast for these stacking boundaries, confirming their diverse morphologies.

In order to further visualize the detailed atomic structures of the stacking boundaries, classical molecular dynamics (MD) are applied to determine the structure based on experimental STEMADF images and compare their stabilities. While it is possible to interpret the position of each atom from regular ADF image patterns for perfect AB stacking, it is challenging to decipher the precise atomic structure from the irregular Moiré patterns such as those shown in Figure 3. Thus, we first construct a reasonable model and relax it to generate the most energetically stable structure. The optimized structures are then used for STEM image simulation and compared to the experimental results.

The gradual and continuous transition from AB to AC stacking can be accomplished in three different scenarios, for stacking boundaries that are parallel to the zigzag direction, armchair direction or a random orientation, respectively: (i) by applying only tensile or compressive strain along the [1, 1] direction (Figure 4), (ii) by applying only shear strain along the [1, 1] direction (Figure 5), or (iii) by applying a combination of normal and shear strain (Figure 6) to the second layer over a transition region of a few nanometers wide.

Figure 4 shows two types of structural models for the zigzag-type stacking boundaries with applied normal strain. Specifically, the in-plane tensile strain stretches the second layer in the transition region (Figure 4a), whereas compressive strain raises the second layer as ripples


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(Figure 4b), which is energetically more favorable than condensing all the carbon atoms in the same plane, as shown by DFT calculations detailed in Figure S8. The width of the transition stacking boundary region is set to be 8 nm (same order of magnitude as measured from TEM and STEM images), and the AB and AC stacking regions (4 nm each) are anchored on both sides. We apply a tensile strain of 1.8% in the stretching model (note that the strain level depends on the width of the transition region), while the compressive strain is mostly released by the ripple. Both models result in an additional shift of 1.42 Å along the [1, 1] direction in the second layer (minimum shift to realize the transition), and generate a relative shift (i.e. a non-zero ∆x1) for the 1.23 Å lattice periodicities between the two graphene layers at the transition region. After MD relaxation, both models generate similar dot-like Moiré patterns in the simulated ADF images (insets), similar to those observed experimentally. Moreover, the total energies for both structures are almost the same (the ripple model is only 2 meV per carbon atom higher than the stretching model). However, MD calculations show that the tensile force induced by the strain in the stretching model (Figure 4a) is nearly 30 times larger than the force in the ripple models (Figure 4b). Therefore, when the constraint of the anchored AB/AC stacking regions is removed in the MD simulation, the second layer in the stretching model tends to shrink to the center in order to release the in-layer tensile force as shown in Supplementary Figure S9. In contrast, the unanchored AB/AC stacking domains remain stable during MD relaxation when ripples are present in the transition regions. Given the large tensile force present in the in-plane tensile strained stacking boundaries (Figure 4a), this type of structure may only exist when the materials are grown under highly nonequilibrium conditions and when there are strong constraints to maintain the AB/AC stacking domains. Therefore, the AB/AC stacking boundaries are more likely to exist in the form of smooth low-energy ripples, especially in regions with a high


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concentration of stacking boundaries (such as the red rectangular regions in Figure 2b) where the accumulation of large tensile forces is energetically undesirable.

Structure models for the armchair-type stacking boundaries with shear strain are shown in Figure 5. In this model, a small amount of shear strain (~ 1.8%) is applied to the second layer, inducing a 1.42 Å shear along the [1, 1] direction (minimum shift to realize the transition) over a transition region of 8 nm with the same area of AB/AC stacking regions (4 nm in width) as in the tensile strain model. After MD relaxation, the AB/AC stacking region can be maintained without anchoring the two sides, suggesting this shear strain level can be easily accommodated at the stacking boundaries. The simulated ADF image (Figure 5c) based on the shear strain model also reproduces the dot-like irregular Moiré patterns in the transition region, as have been observed experimentally (Figure 5d).

Although the AB to AC stacking transition can be achieved by applying solely normal or shear strain along specific directions (either zigzag or armchair direction), the randomly oriented stacking boundaries with diverse irregular Moiré patterns require that both types of strains are jointly present in the transition regions. A general structural model, aiming to model the stacking boundary observed experimentally in Figure 3a, is shown in Figure 6a & 6b, containing both types of strains and optimized by MD calculations. Here the first layer is set to be relatively flat with thermal vibration on the order of ~1 Å 14. A small amount of in-plane shear strain is applied to the second layer along the [1, 1] direction (in this case, a 0.71 Å shear over a 8 nm transition region, inducing ~0.9% shear strain), and a ripple of 7 Å in height shifts the second layer 1.23 Å along the [1, -1] direction and releases most of the compressive strain. The simulated ADF image,


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based on the optimized structural model (Figure 6c), matches well with the experimental filtered ADF image (Figure 6d) extracted from the boundary region in Figure 3a. Moreover, by adjusting the width and the strain profile in the ripple model, a variety of ripple morphologies can be obtained for the stacking boundaries, and the simulated STEM images from these models can well reproduce the irregular Moiré patterns observed experimentally at the stacking boundaries (such as those shown in Figure 3c & 3d), as detailed in the Figure S10. These results confirm that the AB/AC stacking boundaries can be generally described as nm-wide strained ripples with diverse morphologies and strain levels.

In conclusion, by combining high resolution electron microscopy imaging and molecular dynamics simulations, we have shown that the unique AB/AC stacking boundaries in Bernal stacked bilayer graphene are not atomically sharp, but nanometer-wide strained channels, most likely in the form of ripples, with diverse profiles of strain and morphologies. Strain engineering of graphene has been a long sought-after goal for device applications

15, 16

. The omnipresent

strained stacking boundaries can, thus, serve as a reservoir to explore the strain effect on the electronic properties of bilayer graphene, and may provide new functional building blocks for future device fabrication.


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Acknowledgements We thank Dr. Yevgeniy Puzyrev at Vanderbilt University for helpful discussions. This research was supported in part by a Wigner Fellowship through the Laboratory Directed Research and Development Program of Oak Ridge National Laboratory, managed by UT-Battelle, LLC, for the U. S. DOE (WZ), DOE grant DE-FG02-09ER46554 (JL, STP), Oak Ridge National Laboratory's Shared Research Equipment (ShaRE) User Facility Program (JCI), which is sponsored by the Office of Basic Energy Sciences, U.S. DOE, the Office of Basic Energy Sciences, Materials Sciences and Engineering Division, U.S. DOE (ARL, SJP, STP), the National Science Foundation under award number NSF DMR 0845358 and the Army Research Laboratories (WJF,

JK).

This research used resources of the National Energy Research

Scientific Computing Center, which is supported by the Office of Science of the US Department of Energy under Contract No.DE-AC02-05CH11231. Supporting Information Available: Description of the microscopy characterization, density functional calculations, classical molecular dynamics, and supplementary figures. This material is available free of charge via the Internet at http://pubs.acs.org.


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Figure 1: Schematic of AB and AC stackings in BLG. (a) Schematic of different lattice periodicities in monolayer graphene. (b & c) Schematics of AB stacking and AC stacking, respectively. The second layers are colored in pink. The dashed diamonds indicate the unit cells and black arrows are the unit cell vectors. The red arrow indicates the geometrical shift of the second layer with respect to the first layer. The pink strips in Figure 1b & 1c indicate the lattice periodicity of 1.23 Å for the second layer, which is overlapped with the gray strip (lattice periodicity of 1.23 Å for first layer).


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Figure 2: Highly-concentrated stacking boundaries in oBLG. (a) DF-TEM image of a large flake of oBLG, acquired using the diffraction spot (-1,1) (red circle) at zero tilt. (b) False color mapping of AB and AC stacking domains from tilted DF-TEM images taken with diffraction spot (0, 1) (blue circle). The regions with highly-concentrated AB/AC stacking boundaries are highlighted by the red dashed rectangles. (c-e) Higher magnification DF-TEM images of the highlighted region in (a), acquired using diffraction spot (0, 1) at 10˚ (c) and -10˚ (d) tilt, and using diffraction spot (-1,1) at zero tilt (e). The boundaries between AB and AC stacking domains appear as dark lines in Figure e. Scale bars: 2 µm (a,b) and 0.5 µm (c-e).


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Figure 3: Atomic-resolution filtered STEM-ADF images of stacking boundaries. (a) ADF image of a stacking boundary showing a full transition from AB to AC stacking. The transition region is highlighted by the red rectangle. Inset: FFT of the as-acquired image. (b) ADF image of perfect AB stacking. Upper inset: Structural model of perfect AB stacking. The first layer is colored in gray and second in orange. The overlapping sites are highlighted by yellow. Lower inset: Simulated STEM image for perfect AB stacking. (c, d) ADF images showing irregular wiggle-like patterns (c) and square-like patterns (d) at the transition regions of stacking boundaries. Red hexagons represent the orientation of the graphene lattice in the AB stacking regions. Unfiltered images are provided in Figure S5. Scale bars: 1 nm.


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Figure 4: Structural models for stacking boundaries along the zigzag direction with applied normal strain. (a) Side view and top view of the MD optimized in-plane stretching model with AB and AC stacking domains anchored on both sides. 1.8% tensile strain is applied in the transition region with a width of 8 nm. (b) Relaxed structural model of a ripple with the same width and anchored sides, containing compressive strain. The height of the ripple is ~ 7 Å. Inset in both images: simulated ADF images in the corresponding regions. Both models generate similar irregular Moiré patterns to those observed in experiments. Red hexagons represent the orientation of graphene lattice in the ordered AB stacking regions. Scale bars: 0.5 nm.


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Figure 5: Structural model for stacking boundaries along the armchair direction with shear strain. (a, b) Side and top view of the MD optimized model with shear strain along the [1, 1] direction. (c) Corresponding simulated ADF image. Note that only the stacking boundaries parallel to the armchair direction can be constructed by applying shear strain alone. (d) Filtered ADF image of experimentally observed stacking boundary with shear strain. Scale bars: 1 nm.


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Figure 6: Stacking boundaries as strained nm-wide ripples containing both normal and shear strain. (a) Structural model of strained ripples bridging AB and AC stacking domains, optimized by classical molecular dynamics. (b) Top view of the optimized structural model. (c) Simulated STEM-ADF images based on the structural model in Figure a. (d) Similar Moiré patterns observed in experimental STEM images (filtered). Red hexagons represent the orientation of graphene lattice in the ordered AB stacking regions. Scale bars: 1 nm.


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